JPH0641499B2 - Flame-retardant resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame-retardant resin for electrical insulation, and more specifically, it has excellent electrical properties, high heat resistance, and is useful as a laminated board such as a printed wiring board. Flame retardant resin.

[Conventional technology]

Conventionally, 1,2-polybutadiene has electrical properties, especially dielectric constant,
It has a small dielectric loss tangent and is known as a material with excellent heat resistance, moisture resistance, chemical resistance, etc., and has been applied to electronic and electrical parts such as printed wiring boards, coating resin for printed wiring, molding compounds, and insulating varnishes. (For example, JP-A-57-188353 and JP-A-57-188354).

However, as a recent tendency, a certain flame retardant standard is required for electronic and electric parts from the viewpoint of fire prevention, and it is one of the important performances in the development and commercialization thereof. The same applies to printed wiring boards, and in particular flame retardancy such as 94V-0 according to the UL standard is required.

Under such circumstances, it cannot be denied that 1,2-polybutadiene is flammable because its molecular structure is composed only of carbon and hydrogen. Therefore, imparting flame retardancy is an essential condition, but this must be realized without impairing the excellent dielectric properties and heat resistance originally possessed by 1,2-polybutadiene.

[Problems to be solved by the invention]

However, when a conventional flame retardant is simply added to 1,2-polybutadiene to obtain a flame retardant composition, a relatively wide range of flame retardants can be selected. The characteristics are often offset, and the heat resistance and weather resistance are significantly deteriorated. For example, use addition-type flame retardants such as hexabromobenzene, decane bromodiphenyl ether, triphenyl phosphate, and dechlorane, and add flame retardants such as antimony trioxide and triphenylantimony as necessary This method not only impairs the excellent dielectric properties and heat resistance inherent in 1,2-polybutadiene, but also has many drawbacks such as the flame retardant bleeding out on the resin surface.

The present invention is to solve such a problem. Since it forms a stronger polymer network than 1,2-polybutadiene homopolymer, it has excellent heat resistance, is equivalent to the characteristics of conventional glass epoxy substrates, and is difficult. It is an object of the present invention to provide a flame-retardant resin provided with flammability.

[Means for solving problems]

The flame-retardant resin of the present invention has 1,2 having a double bond in the side chain.
100 parts by weight of a butadiene polymer containing 50 mol% or more of butadiene units in the polymer chain, 10 to 100 parts by weight of at least one vinyl compound selected from trihydroxyethyl isocyanuric acid triacrylate and trihydroxyethyl isocyanuric acid trimethacrylate. ,
And the general formulas I to II (Wherein, X is H or CH ₃ or Y Br, A is, -, - O -, - CO -, - SO 2 -, - C (CH 3) 2
_{-, - (CH 2) a} -; m, n and a is an integer of from 1 to 4.. ) At least 1 selected from the compounds represented by
The seed is 25 to 100 parts by weight in the case of the general formula I, the general formula II
In this case, the composition is obtained by blending 25 to 200 parts by weight of a composition with an organic oxide as a polymerization initiator and thermosetting.

In the present invention, a butadiene polymer is a polymer having 50
Polybutadiene with a number average molecular weight of 1,000 to 200,000 consisting of 1,2-butadiene bonds at a mol% or more, and especially 90 mol% or more of 1,2-butadiene bonds of a polymer chain having a number average molecular weight of 10,000 to 200,000 and a melting point. Preferably has a thermoplasticity of 50 to 200 ° C., for example JSR RB-810, RB-820, RB
-830 (manufactured by Nippon Synthetic Rubber Co., Ltd., etc.).

The vinyl compound used in the present invention is trihydroxyethyl isocyanuric acid triacrylate and / or trihydroxyethyl isocyanuric acid trimethacrylate, which is a compound having at least 3 or more vinyl groups in one molecule.

As a reactive flame retardant for imparting flame retardancy, a compound represented by the general formula I
As the 2,4,6-tribromophenyl compound represented by,
For example 2,4,6-tribromophenyl acrylate, 2,4,6-
Examples include tribromophenyl methacrylate, 2,4,6-tribromophenyl allyl ether, and 2,4,6-tribromobenzoate. Examples of the compound having two acryloyl groups or methacryloyl groups represented by the general formula II include, for example, 2,2-bis (4-methacryloyl-3,5-dibromophenyl) propane and 2,2-bis (4- Acryloyl-3,5-
Dibromophenyl) propane, 2,2-bis (4-methacryloyl-3,5-dichlorophenyl) propane, 2,2-bis (4-
Acryloyl-3,5-dichlorophenyl) propane, 4,4 '
-Diacryloyl-3,3 ', 5,5'-tetrabromodiphenylmethane, 4,4'-dimethacryloyl-3,3', 5,5 '
-Tetrabromodiphenylmethane, 4,4'-diacryloyl-3,3'-dichlorodiphenyl sulfone, 4,4'-dimethacryloyl-3,3'-dibromodiphenylbutane,
4,4'-Dimethacryloyl-2,2 ', 3,3', 5,5 ', 6,
6'-octachlorophenyl ether, 4,4'-diacryloyl-3,3 ', 5,5'-tetrachlorodiphenyl and the like.

The compounding ratio of the phthaldiene polymer of the present invention and the vinyl compound is 1 part by weight of the vinyl compound with respect to 100 parts by weight of the butadiene polymer.
It is in the range of 0 to 100 parts by weight. If the compounding ratio of the vinyl compound is less than 10 parts by weight, the adhesive property is deteriorated and the thermal expansion is large, and if it exceeds 100 parts by weight, the dielectric property is deteriorated, which is not preferable. The compounding ratio of the compounds of the general formulas I and II which are reactive flame retardants is 2 parts of the compound of the general formula I with respect to 100 parts by weight of the butadiene polymer.
5 to 100 parts by weight, the compound of general formula II is in the range of 25 to 200 parts by weight. When the compounding ratio of the compounds of the above general formulas I to II is less than 25 parts by weight, it does not contribute to the improvement of flame retardancy, and when it exceeds 100 or 200 parts by weight, the dielectric properties deteriorate.

Next, the flame-retardant resin of the present invention is obtained in the following manner. That is,
At least one selected from a butadiene polymer, trihydroxyethyl isocyanuric acid triacrylate and trihydroxyethyl isocyanuric acid trimethacrylate.
Vinyl compounds and at least one of the compounds of the general formulas I to II are dissolved in an organic solvent such as toluene, xylene, n-hexane, cyclohexane, chloroform, 2-butanone, dimethylformamide or methyl cellosolve. Then, an organic peroxide such as dicumyl peroxide, t-butyl peroxylaurate, t-butyl perbenzoate, or benzoyl peroxide is added as a vinyl polymerization initiator, and the mixture is heated and cured to obtain a flame-retardant resin.

The flame-retardant resin thus produced is used as an electric material such as an insulating material, and is particularly useful for a laminated board such as a printed wiring board. In order to produce a laminated plate, the resin mixture is dissolved in an organic solvent, and an impregnating varnish prepared by adding an organic peroxide thereto is used as a base material, for example, glass fiber, synthetic fiber or other organic or inorganic fiber. Impregnate the used cloth or non-woven fabric,
Evaporate the solvent at 80-180 ° C for 5-60 minutes to make a prepreg sheet. If necessary, several prepreg sheets are superposed and laminated at a predetermined temperature and pressure to obtain a laminated plate. Further, a copper clad laminate can be obtained by laminating copper foil on one surface or both surfaces of this laminate and simultaneously laminating and molding the same. The laminated board thus obtained is
As will be described later, it has various properties such as excellent heat resistance and dielectric properties, and is particularly excellent in heat resistance and flame retardancy.

The flame-retardant resin of the present invention is a butadiene polymer containing 50% or more of 1,2-butadiene units having a double bond in the side chain in the polymer chain, trihydroxyethyl isocyanuric acid triacrylate and trihydroxyethyl isocyanuric acid trimethacrylate. A resin obtained from at least one vinyl compound selected from the following and at least one of the 2,4,6-tribromophenyl compounds represented by the general formula I or the compound represented by the general formula IV. A highly balanced polybutadiene network is cross-linked with a highly flame-retardant compound and a specific vinyl compound in a well-balanced manner, so that it has the same properties as conventional epoxy resins and has significantly improved heat resistance and flame retardancy. It is thought to improve.

〔Example〕

 The present invention will be specifically described below with reference to examples.

Example 1 Syndiotactic 1,2-polybutadiene (JSR RB-81 in which about 90 mol% of the polymer chains consist of 1,2-butadiene bonds)
0, manufactured by Nippon Synthetic Rubber Co., Ltd., trade name, number average molecular weight of about 15
10,000) 80 g, trihydroxyethyl isocyanuric acid triacrylate (FA-731A, manufactured by Hitachi Chemical Co., Ltd., trade name) 20
35 g of 2,4,6-tribromophenyl acrylate and 5 g of dicumyl peroxide were dissolved in 400 g of toluene and poured into a mold made of aluminum. After degassing under vacuum at 60 ° C., the solvent was evaporated, and then heat curing was performed from 120 ° C. to 180 ° C. in 30 ° C. steps for 2 hours each, for a total of 6 hours. After cooling, it was taken out of the mold and the dielectric constant of the obtained cured product,
The dielectric loss tangent, the coefficient of thermal expansion and the glass transition point were measured, and the results are shown in Table 1.

Example 2 Syndiotactic 1,2-polybutadiene in which about 90 mol% of polymer chains are 1,2-butadiene bonds (supra) 85
g, trihydroxyethyl isocyanuric acid trimethacrylate (FA-731M, manufactured by Hitachi Chemical Co., Ltd., trade name) 15 g, 2,
55 g of 2-bis (4-methacryloyl-3,5-dibromophenyl) propane (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) and 2 g of dicumyl peroxide were dissolved in 430 g of toluene and poured into a mold made of aluminum. After degassing under vacuum at 60 ° C., the solvent was evaporated, and then heat curing was performed from 120 ° C. to 180 ° C. in 30 ° C. steps for 2 hours each, for a total of 6 hours. After cooling, the product was taken out from the mold and the properties of the obtained cured product were measured in the same manner as in Example 1, and the results are shown in Table 1.

Example 3 Syndiotactic 1,2-polybutadiene (supra) 90 in which about 90 mol% of the polymer chains consist of 1,2-butadiene bonds
g, trihydroxyethyl isocyanuric acid triacrylate (above) 10 g, 2,4,6-tribromophenyl acrylate 35 g and dicumyl peroxide 6 g in toluene
It was dissolved in 450 g and poured into an aluminum mold. 60
After evaporating the solvent while degassing under vacuum at 120 ° C,
C. and 150.degree. C. for 2 hours each, and 180.degree. C. for 1.5 hours, for a total of 5.5 hours. After cooling, the product was taken out from the mold and the properties of the obtained cured product were measured in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 100 g of 1,2-polybutadiene described in Example 1 and 2.5 g of dicumyl peroxide were dissolved in 500 g of toluene and poured into a mold made of aluminum. Then, the same operation as in Example 1 was performed to obtain a cured product. The characteristics of this cured product are shown in Example 1.
The measurement was performed in the same manner as above, and the results are shown in Table 1.

Comparative Example 2 100 g of a bisphenol A type epoxy resin (DER-332, manufactured by Dow Chemical Co., trade name, number average molecular weight of about 350) and 4 g of dicyandiamide were dissolved in 40 g of dimethylformamide and poured into a mold made of aluminum. Thereafter, a cured product was obtained by the same operation as in Example 1, and the characteristics were measured in the same manner. Table 1 shows the results.

Example 4 70 g of 1,2-polybutadiene described in Example 1, 30 g of trihydroxyethyl isocyanuric acid triacrylate, 2,4,6-
35 g of tribromophenyl acrylate and 4 g of dicumyl peroxide were dissolved in 350 g of toluene to prepare a varnish. A glass cloth was impregnated with this varnish and dried at 130 ° C. for 10 minutes to obtain a tack-free prepreg sheet.

Next, eight prepreg sheets were stacked, copper foils were stacked on the upper and lower sides, and press-molded at 180 ° C. and 40 kg / cm ³ for 90 minutes to obtain a copper-clad laminate. The dielectric constant, dielectric loss tangent, solder heat resistance, and trichlene resistance of the obtained laminated plate were measured, and the results are shown in Table 2.

Example 5 90 g of 1,2-polybutadiene described in Example 2, 10 g of trihydroxyethyl isocyanuric acid trimethacrylate, 2,2-
Toluene was added with 55 g of bis (4-methacryloyl-3,5-dibromophenyl) propane and 3 g of dicumyl peroxide.
It was dissolved in 450 g to give a varnish. A glass cloth was impregnated with this varnish and dried at 140 ° C. for 5 minutes to obtain a prepreg sheet having no tackiness.

Next, eight prepreg sheets were stacked, copper foils were stacked on the upper and lower sides, and press-molded at 180 ° C. and 40 kg / cm ³ for 90 minutes to obtain a copper-clad laminate. The characteristics of the obtained laminate were measured in the same manner as in Example 4, and the results are shown in Table 2.

Example 6 95 g of 1,2-polybutadiene described in Example 1, 5 g of trihydroxyethyl isocyanuric acid triacrylate, 2,4,6-
35 g of tribromophenyl acrylate and 6 g of dicumyl peroxide were dissolved in 480 g of toluene to prepare a varnish. After that, the same operation as in Example 4 was performed, and the characteristics of the obtained laminate were measured in the same manner, and the results are shown in Table 2.

Comparative Example 3 100 g of 1,2-polybutadiene described in Example 1 and 2.5 g of dicumyl peroxide were dissolved in 500 g of toluene to prepare a varnish. Impregnate this varnish into glass cloth and
It was dried for 0 minutes to give a prepreg sheet having no tackiness. After that, the same operation as in Example 4 was performed, and the characteristics of the obtained laminate were measured in the same manner, and the results are shown in Table 2.

Comparative Example 4 100 g of the epoxy resin described in Comparative Example 2 and 4 g of dicyandiamide were dissolved in 40 g of dimethylformamide to prepare a varnish. Glass cloth is impregnated with this varnish, and it is heated at 150 ° C for 5
After drying for a minute, a prepreg sheet having no tackiness was obtained.
After that, the same operation as in Example 4 was performed, and the characteristics of the obtained laminate were measured in the same manner, and the results are shown in Table 2.

From the results shown in Tables 1 and 2, it became clear that the present invention can remarkably improve the characteristics of the comparative example and sufficiently satisfy the required characteristics.

〔The invention's effect〕

According to the present invention, at least one vinyl compound selected from a butadiene polymer containing 50 mol% or more of 1,2-butadiene units, trihydroxyethyl isocyanuric acid triacrylate and trihydroxyethyl isocyanuric acid trimethacrylate, and a general formula: By reacting the compound represented by I or II to form a stronger polymer network than the polybutadiene homopolymer, it has excellent heat resistance and low thermal expansion, and is equivalent to the characteristics of conventional epoxy resin substrates. In addition, the flame retardancy can be significantly improved, and the industrial utility value is very large.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Seiji Oka 8-1-1 Tsukaguchi Honcho, Amagasaki City, Hyogo Prefecture Sanryo Electric Co., Ltd. Production Technology Laboratory (72) Inventor Mitsuhiro Nogaki 8 Tsukaguchi Honcho, Amagasaki City, Hyogo Prefecture 1-1-1 Sanritsu Electric Co., Ltd., Production Technology Laboratory (56) Reference JP-A-49-29335 (JP, A) JP-A-49-18936 (JP, A) JP-A-47-34985 (JP, A) Japanese Patent Sho 58-1123 (JP, B2) Japanese Patent Sho 56-9525 (JP, B2)

Claims (2)

[Claims] 1. 100 parts by weight of a butadiene polymer containing 50 mol% or more of 1,2-butadiene unit having a double bond in a side chain in a polymer chain, trihydroxyethyl isocyanuric acid triacrylate and trihydroxyethyl isocyanuric acid triester. 10 to 100 parts by weight of at least one vinyl compound selected from methacrylate, and general formulas I to II (Wherein, X is H or CH ₃ or Y Br, A is, -, - O -, - CO -, - SO 2 -, - C (CH 3) 2
_{-, - (CH 2) a} -; m, n and a is an integer of from 1 to 4.. ) At least 1 selected from the compounds represented by
The seed is 25 to 100 parts by weight in the case of the general formula I, the general formula II
In the case of, a flame-retardant resin composition comprising 25 to 200 parts by weight of a composition and an organic oxide as a polymerization initiator. 2. A butadiene polymer having a number average molecular weight of 1,00.
The flame-retardant resin composition according to claim 1, which is 0 to 200,000.